Substituted amino-1, 3, 5-triazines



United States Patent 3,310,557 SUBSTITUTED AMINO-1,3,5-TRIAZINES v AloisKleemann, Basel, Switzerland, assignor to Geigy Chemical Corporation,Greenburgh, N.Y., a corporation of Delaware No Drawing. Filed May 28,1965, Ser. No. 459,936 Claims priority, application Switzerland, June 2,1964, 7,188/64; May 3, 1965, 6,130/65 9 Claims. (Cl. 260249.6)

The present invention concerns new N -substituted2-arnino-l,3,5-triazines, a process for the production thereof, theiruse for making dyeings and plastics fast to gasfading, as well as, asindustrial products, the dyeings or plastics rendered fast to gas fadingwith the aid of these compounds.

It is known that dyeings of cellulose esters, cellulose ethers andpolyurethanes produced with certain dyestuffs undergo an undesirablechange in shade in an atmosphere which contains combustion gases. It isalso known that certain plastics, namely elastomeric polyurethanes aredeteriorated by the attack of combustion gases, which deteriorationbecomes noticeable by :a yellowing of these materials.

It has now been found that changes of such dyeings of cellulose esters,cellulose ethers and polyurethanes or the deterioration and particularlyyellowing of elastomeric polyurethanes caused by combustion gases can bere duced or prevented entirely by applying to these materials protectiveamounts of N -substituted 2-amino-1,3,5-triazi-nes of the formula.

In these formulae:

R R and R each represent hydrogen or a lower alkyl or an aralkylespecially a benzyl group, or each of the pairs R and R or R and Rrepresents an nee-lower alkylene group, especially an ethylene group,

R R R and R each represent hydrogen or a lower alkyl group, or each ofthe pairs R and R or R and R represents an a,8-n-butylene or loweralkyl-substituted a,5-n-butylene group,

R represents unsubstituted aralkyl especially benzyl or aryl, especiallyphenyl, or an aralkyl or aryl radical substitued in the ring bynon-ionic, noncolor imparting substituents, or it represents acycloalkyl radical, especially cyclohexyl,

n represents 1 or 2, and

X and X each indepedently represents chlorine or bromine or one of theradicals R ,O-R ,-fiSR or wherein R represents an unsubstituted loweralkyl, aralkyl, especially benzyl or aryl, especially phenyl radical oran alkyl, aralkyl or aryl radical substituted by non-ionic, non-coloringsubstituents, or it represents a cycloalkyl radical, especiallycyclohexyl, and

R and R are hydrogen or have each the same meaning as R and R can alsorepresent a carbacyl group, especially a lower alkanoyl group or benzoylgroup.

Preferably X and X both represent NH Active compounds according to theinvention are ob- "ice tained by reacting 1 mol of cyanuric chloride orbromide, in any order desired, with (a) One mol of an amine of Formula Iwherein Hal represents chlorine, bromine or iodine, particularly bromineor iodine, or with a compound of Formula III HOR (III) or an alkalimetal salt thereof, or with a compound of FormulaIV PIS-R (IV) or awater soluble salt thereof, or with a compound of FormulaV R10 HN u (V)and, optionally, further (0) With one mol of a compound of Formula H,III, IV or V, to form a compound of Formula VI.

Preferably 1 mol cyanuric chloride or bromide is reacted With 1 mol ofan amine of the Formula I and two mols of ammonia.

If R R R R R R or R represents a lower alkyl group then it is mainly themethyl or ethyl group. If R R or R represents an aralkyl group then itis prefer ably the benzyl group.

If each of the pairs R and R or R and R repreesnts an u,fl-alkylenegroup, then they are chiefly the 1,2-ethylene group.

If each of the pairs R and R or R and R represents an afi-alkylenegroup, then this is preferably the 1,4- butylene group.

The new compounds of Formula VI are well crystallized colourlesssubstances. They impart remarkable resistance to gas fading to celluloseester and cellulose ether dyeings and also to plastics, chieflyelastomeric polyurethanes, which are sensitive to combustion gases.

To improve the fastness to gas fading of the dyed plastics of the typesmentioned, the :N -substituted 2-amino-1, 3,5-triazines according to theinvention can be used before, during or after the dyeing process. Fibresor fabrics made of cellulose esters or ethers or of polyurethanes can bepretreated With a solution or dispersion of the compounds according tothe invention and then dyed; also, however, the aminotriazines mentionedcan be added to the dyebath, and the dyeing and making fast to gasfading can be performed in one process; finally, dyed cellulose ester,ether or polyurethane materials can also be after-treated with solutionsor dispersions of these compounds.

To protect elastomeric polyurethanes, preferably in the form of fibressuch :as spandex fibres (long chain synthetic polymer containing atleast of polyurethane segments) from injury due to gas fading,particularly to reducing the yellowing thereof, these polyurethanes aretreated with a solution or dispersion of N substituted2-amino-l,3,5-triazines according to the invention.

The new aminotriazines of Formula VI can also be incorporated into thespinning masses.

Cellulose ester, and cellulose ether materials which have been treatedwith the compounds of Formula VI according to the invention are moreresistant to the effect of industrial fumes, namely nitric oxides. Alsoelastomeric polyurethanes treated with the aminotriazines of Formula VIaccording to the invention are substantially protected from yellowingdue to industrial fumes.

The compounds of Formula VI according to the invention barely affect thelight fastness of the dyeings on the materials mentioned.

As aralkyl radical, R R R and R are mainly a benzyl radical, as arylradical they are particularly a phenyl radical and as cycloalkyl radicalthey are chiefly the cyclohexyl radical.

Examples of non-ionic and non-colouring substituents in aromatic ringsof R R R and R are halogen such as fluorine, chlorine or bromine, lowalkyl groups such as the methyl, ethyl or butyl group or low alkoxygroups such as the methoxy, ethoxy or butoxy group or aryloxy groups.

Alkyl groups in the positions of R R and R preferably contain 1-4 carbonatoms and are advantageously unsubstituted; however, if they aresubstituted, then the principal substituents are low alkoxy groups suchas the methoxy or ethoxy group or halogens up to the atomic number 35such as fluorine, chlorine or bromine, or the cyano group.

Examples of carbacyl groups in the position of R are low al'kanoylgroups such as the acetyl or propionyl group, or aroyl groups, e.g. thebenzoyl group.

In preferred compounds of Formulae I and VI, each of R and R representshydrogen, R and R together represent the 1,2-ethylene radical and n is1; or R and R each represents hydrogen and R and R each representshydrogen or the methyl group, and n is 1; in these cases, R represents aphenyl radical optionally substituted by non-ionic and non-colouringsubstituents, particularly it represents the unsubstituted phenylradical or in the second case also the benzyl radical.

X and X are preferably the amino group. Starting materials of FormulaeI, II, III, IV and V are known or can be produced by methods known perse.

Examples of amines of Formula I are: N-cycloalkylethylenediamines suchas N-cyclohexyl-ethylenediamine, N-aralkyl-ethylenediamines such asN-benzylor N-(2-, 3- or 4-methylbenzyl)-ethylenediamine, orN-aryl-ethylenediamines such as N-phenylor N-(2-, 3- or4-chlorophenyl)-ethylenediamine, or N,N'-di-alkyl- (such asN,N'-dimethylor N, N'diethyl-) N-cycloalkyl-ethylene- 'diamines,N,N'-dialkyl- Naralkylor -N-aryl-, particularly-N-phenyl-ethylenediamines, or l-amino-Z-N-cycloheXyl-, 1-amino 2 Naralkylor l-amino-Z-N-arylamino cyclohexanes, or l-amino 2 (N-alkyl Narylamino)-cyclohexa-nes, in the latter case, e.g. l-amino-2- (N-methyl-N phenylamino)-cyclohexane, or N-cycloalkyl-, N-aralkylor N-aryl-, thenparticularly N-phenylpiperazines, or N-aryl-, particularly N phenyl N(flalkylaminoalkyl)-pipera:zines, e.g. N-phenyl N-(,B-alkylaminoethyl)-piperazines.

Preferred starting materials of Formula I are N-phenylp-iperazines orN,N'-dialkyl-N-pheny-l-ethylenediamines, then particularlyN,N'-dimethyl-N-phenyl-et-hylenediamine.

In the production of N -substituted 2-amino-l,3,5,-triazines accordingto the invention, the triazine compound is reacted advantageously in thefirst step with the amine of Formula I or with the Grignard compound ofFormula II, in the second step with the amine of Formula V or with theamine of Formula I, and in the third step with the hydroxyl or mercaptocompound of Formula III or IV.

The reaction of the triazine compound with the reaction partners asdefined is performed in the first step at about l0 C., in the secondstep at about 0-60 C. and in the third step at temperatures of over 60C.

The reaction with the Grignard compound of Formula II is performedadvantageously in anhydrous, inert organic solvents, particularly thosecontaining oxygen, such as in an ether, e.g. a dialkyl ether such asdiethyl ether, or a cyclic ether such as dihydrofuran.

The reaction with the amines of Formula I or V is preferably performedin an organic solvent and in the presence of an agent buffering acid.Suitable solvents for the reaction are, e.g. unsubstituted orchlorinated or nitrated aromatic hydrocarbons such as benzene, tolueneor xylenes, or chlorobenzene or 1,2-dichlorobenezene or nitrobenzene, orchlorinated aliphatic hydrocarbons such as tetrachloroethylene. However,the reaction can also be performed in aqueous or aqueous-organicdispersion. Mainly excess amine or alkali hydroxides such as sodium orpotassium hydroxide serve as principal acid buffering agents.

Hydroxyl compounds of Formula III are preferably used in excess. If theyare reacted in the first step with the cyanuric chloride or bromide, thereaction is advantageously performed in the presence of agents having aweak alkaline reaction such as alkali bicarbonates; if they are reactedin the second or third step then equivalent amounts of their alkalicompounds are used, e.g. the sodium or potassium alcoholates orphenolates, an excess of the organic hydroxyl compounds of Formula IIIadvantageously serving as solvent or flux.

If mercapto compounds of Formula IV are used, then advantageouslyequivalent amounts of their alkali metal salts in organic solution areused. Organic solvents which are advantageously used for this purposeare water soluble alcohols, i.e. low alkanols such as methanol orethanol, or alkylene glycol monoalky-l ethers such as ethylene glycolmonomethyl ether.

The following examples illustrate the invention. The temperatures are indegrees centigrade. C.I. means Color Index, published by the Society ofDyers and Colourists, Dean House, Piccadilly, Bradford, Yorkshire,England, with acknowledgement to the American Association of TextileChemists and Colorists, Lowell, Mass, U.S.A., abs. means absolute.

Example 1 lTIHa o Cl t t fi e N CHZ-OHz Cyanuric chloride is convertedinto 2,4-diamino-6- chloro-1,3,5-triazine with ammonia by methods knownper se.

29 g. of 2,4-diamino-6-chloro-1,3,5,-triazine and 43 g. ofN-(3-chlorophenyl)-piperazine in 600 ml. of ethanol are refluxed. Afterthe original alkaline reaction has disappeared, 26 g. of concentratedsodium hydroxide solution are added to the mixture dropwise. The mixtureagain reacts alkaline to phenolphthalein. It is refluxed for anotherhalf hour, then filtered and the filtrate is cooled. The product whichcrystallises out is filtered off and washed with a little ethanol.According to elementary analysis by combustion the compound is that ofthe formula given above. This sub-stance melts with 1 mol of crystalalcohol at 186.

The end product gives cellulose acetate dyeings good resistance to gasfading.

If in the above example, instead of the 43 g. of N-(3-chlorophenyl)-piperazine, the equivalent amounts of one of the aminesgiven in column II of the following Table 1 are used, then compoundshaving similar activity are obtained.

TABLE 1 II III E x. No. Amine MP. of end product, degreesN-(4-ehloropheny1)-piperazine 240 N (3, 4dichloropheny1)-piperazi 224 N-(2-fluorophenyl)-piperaziue 186 N- (3-fluorophenyl)-p1perazme 220 N-(Mluorophenyl) -p1per azme. 231 N- (3bromopheny1)-piperazine 182 N-(S-iodophenyl)-piperazine 1 134 N- (3-trifluoromethylphenyl)-piperazine159 N- (3-trifluoromethyl-tchlorophenyl)-p i p e r avine 198200N-(2methylphenylg-piperazine 1 136 N-(B-methylphenyl -piperazine 201 N-(4n1ethylpl1enyl) -piperazine 219 N- (4-phenoxyphenyl)-piperazine- 164N- (4-phenylthiophenyl) -piperazine 1 100-105 N-naphthyl- (1)-piperazine 25 N-eyelohexyl-piperazine. 205 N-benzy1-piperazine.-178-180 1 Decomposition.

29 g. of 2,4-diamino-6-chloro-triazine (produced by reacting cy-anuricchloride with ammonia in the known manner) are suspended in 600 ml. ofethanol and 38 g. of N-phenyl-N,N-dimethyl-ethylene-diamine are added.The mixture is then refluxed. As soon as the alkaline reaction of themixture can only be determined on litmus paper, 26 g. of concentratedsodium hydroxide solution are added dropwise while stirring. Thereaction mixture is then boiled until it becomes clear. While still hot,precipitated sodium chloride is filtered off. On cooling the filtrate,the compound of the above formula crystallises out. It melts at 175-177and gives cellulose acetate dyeings good resistance to gas fading.

Example 20 If in Example 19, instead of the 38 g. of N-phenyl-N,N'-dimethyl-ethylene-diamine, the equivalent amount of N phenyl'N,N',N"-trimethyldiethylenetriamine is used, then by the proceduregiven in the example, the compound of the formula is obtained, M.P.l33134. It also gives cellulose dyeings good fastness to gas fading.

By repeating Example 19, but using instead of the aforesaid diamine anequivalent amount of N -phenyldiethylenetriamine, there is obtained thecompound of the formula By repeating Example 19, but using instead ofthe aforesaid diamine an equivalent amount of the triamine of theformula the correspondingly substituted melamine compounds falling underFormula VI are obtained.

3 0 g. of N-phenyl-ethylenediamine are added to a suspension of 29 g. of2,4-diamino-6-chloro-triazine in 550 ml. of ethanol, and the mixture isrefluxed. As soon as the strong alkaline reaction of the mixture becomesweaker, 26 g. of concentrated sodium hydroxide solution are addeddropwise while stirring whereupon the mixture is refluxed until allorganic material has dissolved. While still hot, sodium chloride isfiltered off. On cooling, the compound of the above formula crystallisesout of the filtrate. It melts at -181 and it makes cellulose acetatedyeings which are susceptible to gas fading more resistant to industrialfumes.

Example 22 22 g. of 2,4-diamino-6-chloro-triazine are suspended in 300ml. of dioxan. 37 g. of N-phenyl-N'-(,B-methylaminoethyl)-piperazine areadded to this suspension and the whole is refluxed while stirring. Whenthe reaction mixture has only a slightly alkaline reaction, 20 g. ofconcentrated sodium hydroxide solution are added dropwise. The mixtureis heated untilthe reaction is completed. The precipitated sodiumchloride is then filtered off and the filtrate is concentrated whereuponthe compound of the above formula crystallises out. This compound meltsat 241 and gives cellulose acetate dyeings good resistance to gasfading.

If instead of the 37 g. of N-phenyl-N-(fi-methylaminoethyl)-piperazine,the equivalent amount of one of the amines mentioned in column II of thefollowing Table 2 is used and otherwise the procedure given in theexample is followed, then compounds having similar activity areobtained.

' solution are slowly added dropwise.

.7 Example 25 l Hz Hz A solution of 330 g. of N-phenyl-piperazine in1500 ml. of benzene is added dropwise while stirring well at to asolution or 184 g. of cyanuric chloride in 1500 ml. of benzene. Thereaction mixture is then filtered, the filtrate is concentrated underreduced pressure and cooled. The N-[2,4-dichloro-l,3,5-triazinyl (6)] Nphenylpiperazine which precipitates is filtered off, washed with alittle benzene and reacted with alcoholic ammonia solution at 140 underpressure.

The end product of the above formula rnelts at 193 and gives celluloseacetate dyeings which are sensitive to industrial fumes a noticeableresistance to gas fading.

Example 26 184 g. of cyanuric chloride are dissolved in 1500 ml. ofbenzene. A solution of 400 g. of 3-chlorophenyl-piperazine in 1500 m1.of benzene is added dropwise at 10 while stirring. A precipitate soonforms. On completion of the dropwise addition, the mixture is stirredfor another hour and then filtered. On concentrating the filtrate,N-[2,4-dichloro-1,3,5-triazinyl-(6)]-N-(3 chlorophenyl)-piperazine isobtained. On reacting this compound with alcoholic ammonia solution asdescribed in Example 25, the end product of the formula given in Example1 is obtained.

29 g. of 2,4-diamino-6-chloro-1,3,5-triazine, produced according toExample 1, are suspended in 600 ml. of ethanol and 40 g. of2-benzylamino-3-amino-butane are added while stirring. The reaction massis then brought to the boil and 26 g. of concentrated sodium hydroxideOn completion of this addition, the mixture is boiled until it has onlya weakly alkaline reaction to litmus paper. Undissolved sodium chlorideis then filtered off hot. After evaporating off the solvent in vacuo,the compound of the above formula is obtained.

If in the above example, equivalent amounts of 2-benzyl-amino-3-aminopropane,2-benzylamino-3-(pi-ethylamino)-amino-butane or2-amino-3-(N-benzyl-ethylenediamino)-butane are used then compoundsgiving similar fastness to gas fading are obtained.

Example 28 37 g. of N-benzyl-N-methyl-ethylenediamine are added to asuspension of 29 g. of 2,4-diamino-6-chloro-1,3,5- triazine, producedvaccording to Example 1, in 500 ml. of butanol. The reaction mixture isbrought to the boil and 26 g. of concentrated sodium hydroxide solutionare slowly added dropwise so that the mass always has phenolphthaleinalkaline reaction. On completion of the addition, boiling is continueduntil the reaction of the mixture is only alkaline to litmus paper. Allorganic substance has then been dissolved. Precipitated sodium chlorideis then filtered off and the filtrate is evaporated to dryness in vacuo.The compound of the above formula is obtained in this way.

If in the above example, equivalent amounts of N,N- dibenzylethylenediamine, N,N dibenzyl N methylethylenediamine, N benzyl N methylN methylethylenediamine or N,N'-dibenzyl N ethyl ethylenediamine areused then reaction products which give the same good fastness to gasfading are obtained.

Example 29 CH C H 37 g. of cyanuric chloride are dissolved in 300 ml. ofbenzene and the solution is cooled to 8-l0. The solution of 66 g. ofN,N-dimethyl-N-phenyl-ethylenediamine in 300 ml. of benzene is addeddropwise thereto at 8 while stirring. A precipitate soon forms. Oncompletion of the dropwise addition, the reaction mixture is stirred for2 hours at room temperature. The precipitate is then filtered off undersuction, washed with a little benzene and the filtrate is concentratedin vacuo to half its volume. After standing for a few hours, the endproduct crystallis-es out. It has the above formula. It is filtered offunder suction and. dried in vacuo at 70. The product melts at 118-120.It gives cellulose acetate and cellulose ether dyeings good resistanceto industrial fumes.

End products having a similar action are obtained if, instead of the 37g. of cyanuric chloride, equimolar amounts of cyanuric bromide are usedwith otherwise the same procedure.

If, instead of the 66 g. of N,N'-dimethyl-N-phenylethylenediamine,equimolar amounts of the compounds listed below are used and otherwisethe procedure given in the example is followed, then end products arealso obtained which make cellulose acetate dyeings resistant toindustrial fumes.

(a) N,N-dimethyl-N-(2-, 3- or 4-methylphenyl)-ethylenediamine,

(b) N-(2-, 3- or 4-chlorophenyl)-ethylenediamine,

(c) N,N-diethyl-N-phenyl-ethylenediamine,

(d) 1 amino 2 (N methyl N phenylamin0)- cyclohexane,

(e) N-phenyl-N'- (,B-methylaminoethyl) -piperazine,

(f) N,N-dimethyl-N-cyc-lohexyl-ethylenediamine,

(g) N,N'-dimethyl-N-benzyl-ethylenediamine,

(h) N,N-dimethyl-N-(2-, 3- or 4-chlorobenzyl)-ethylenediamine,

(i) N,N-dibenzyl-ethylenediamine,

(k) N,N-dibenzyl-N'-methyl-ethylenediamine,

(l) N,N-d'i B-phenyl-ethy'l) -N-methyl-ethylenediamine,

(m) 4-phenyl-2,3-di-isopropyl-piperazine,

(n) 4 phenyl 1 ([3 methylaminoethyl) 2 methyl-piperazine,

(o) N-(4-methyl-benzyl)-N-methyl-ethylenediamine,

(p) N (4 =chlo1'o methyl benzyl)-N-methylethylenediamine.

Example 30 1 The solution of 29 g. of the amino dichlorotriazine in 200ml. of ethanol obtained according to Example 29 is saturated with 20 g.of ammonia and heated in an auto- 9 clave for 3 hours at 60. Theprecipitate formed is then filtered off under suction and recrystallisedfrom methanol. In this way the end product of the above formula isobtained, M.P. 150. It gives elastomeric polyurethane .good resistanceto industrial fumes.

If instead of 20 g. of ammonia, equimolar amounts of the followingamines are used, then with otherwise the same procedure, end productswhich can give fastness to industrial fumes are obtained.

(a) Methylamine,

(b) Ethylamine,

(c) Dimethylamine,

( d) fl-cyanethylamine,

(e) Cyclohexylamine,

(f) Benzylamine,

(g) 4-methylbenzylamine,

(h) Z-methylphenylamine.

Example 3] CH CH3 (ll-NH] l O C3117 44 g. of the diamino chlorotriazineproduced according to Example 30 are added to a solution of 3.4 g. ofsodium in 350 ml..of abs. n-propanol. The mixture is then refluxed for 3hours, in which the mimosa alkaline reaction disappears and aprecipitate of sodium chloride is formed. The sodium chloride isfiltered off from the hot mixture and the filtrate is evaporated todryness in vacuo. The residue is recrystallised from n-hexane. The endproduct of the above formula is obtained, M.P. 93, which giveselastomeric polyurethane good fastness to industrial fumes.

End products also giving good fastness to industrial fumes are obtainedif, instead of n-propanol, equimolar amounts of one of the organichydroxyl compounds given below is used and otherwise the same procedureas given in the example is followed.

(a) Methanol,

(b) Ethanol,

(c) Ethyleneglycol monomethyl ether,

(d) Cyclohexanol,

(e) Benzyl alcohol,

(f) 2-methylbenzyl alcohol,

(g) Phenol,

(h) 4 methylphenol.

Example 32 CH3 CH3 3.4 g. of sodium are dissolved in 250 ml. of abs.npropanol. A solution of g. of ethyl mercaptan in 100 ml. of abs.propanol is added to this solution. 44 g. of the diamino chlorotriazineproduced according to Example 30 are added to this mixture and themixture is boiled for 2 hours until the reaction mass no longer has amimosa alkaline reaction. The precipitated sodium chloride is thenfiltered off and the filtrate is evaporated to dryness in vacuo. Theresidue is recrystallised from cyclohexane. The end product of the aboveformula is obtained in this way, M.P. 97. It gives cellulose acetate andcellulose ether dyeings good fastness to gas fading.

If, instead of 10 g. of ethyl mercaptan, equimolar amounts of one of themercaptans listed below are used,

Example 33 0 H3 CH3 6.9 g. of sodium are dissolved in 350 ml. of abs.ethanol. 28 g. of phenol and 46 g. of the amino dichlorot-riazineobtained according to Example 29 are added to this solution. Thereaction mixture is then boiled for 4 hours during which time sodiumchloride precipitates. The sodium chloride is filtered off and thefiltrate is allowed to cool whereupon the end product of the aboveformula crystallises out. It is filtered off under suction and dried inVacuo at 70.

It gives cellulose acetate dyeings good fastness to gas fading.

End products which also give good fastness to gas fading are obtained byreplacing the 28 g. of phenol by equimolar amounts of one of the organichydroxyl compounds mentioned in Example 31 under (a), (b), (c), 0r

Example 34 CH CH N 36 g. of N,N'-dimethyl-N-phenyl-ethylenediamine, 600ml. of ethanol and 35 g. of 2,4-bis-(N-methylamino)-6- chlorotriazine,produced by reacting cyanuric chloride with 2 mols of methylamine, areboiled together. When the mixture no longer has a phenolphthaleinalkaline reaction, 26 g. of sodium hydroxide solution are slowly addeddropwise thereto. After boiling for 6 hours, the mixture has a neutralreaction. Precipitated sodium chloride is filtered off and the filtrateis evaporated to dryness in vacuo. An oil remains which slowlysolidifies. It is crystallised from methanol and so the end product ofthe above formula is obtained, M.P. It gives cellulose acetate andcellulose ether dyeings good fastness to industrial fumes.

Example 35 OII2 OH3 GHQ-om N (IL-Cl 1 1" volume of about 800 ml. Afterallowing to stand a little, the end product of the above formulaseparates out of the filtrate in the form of beautiful crystals. Itmelts at 162.

This compound gives cellulose acetate dyeings good fastness to gasfading.

End products which also give good fastness to gas fading are obtainedif, in the above example, instead of the 350 g. of N-phenyl piperazine,equimolar amounts of one of the compounds listed below are used andotherwise the procedure given in the example is followed.

(a) N-(2-, 3- or 4 methylphenyl)-piperazine,

(b) N-benzyl piper-azine,

(c) N-cyclohexyl piperazine,

(d) N- (N-phenyl-N-methyl-aminoethyl) -piperazine.

If, in the above example, cyanuric bromide in benzene solution isreacted with N-phenyl piperazine or with equimolar amounts of the baseslisted above, then substituted amino dibromotriazines having a similaraction are obtained.

Example 36 31 g. of the amino dichlorotriazine obtained according toExample 35, 200 ml. of ethanol and g. of gaseous ammonia are heated inan autoclave for 3 hours at 60. On completion of the reaction, theprecipitate formed is filtered off, it is taken up in hot benzene, thehot benzene solution is filtered and the filtrate allowed to cool. Thecompound of the above formula precipitates in the form of fine crystals.This compound melts at 193. The product gives good fastness to gasfading to elastomeric polyurethane.

Compounds which also give good fastness to gas fading are obtained ifthe 20 g. of ammonia used are replaced by equimolar amounts of one ofthe amines given in Example under (a)(h).

Example 37 3.4 g. of sodium are dissolved in 300 ml. of abs. ethanol andthen 44 g. of the diamino chlorotriazine obtained according to Example36 are added to this solution. A clear solution is obtained. Thissolution is then refluxed for 4 hours during which the mimosa alkalinereaction gradually disappears and a precipitate of sodium chloride isformed. The hot solution is then filtered. On cooling, the compound ofthe above formula crystallises from the filtrate. It is filtered oifunder suction, washed with a little methanol and dried in vacuo at 70.It melts at 140. It gives cellulose acetate dyeings good resistance toindustrial fumes.

Compounds which also give good fastness to industrial fumes are obtainedif the 300 ml. of ethanol are replaced by equimolar amounts of one ofthe organic hydroxyl compounds given in Example 31 under (a) and (c)(h).

Example 38 36 g. of N-phenyl piperazine are dissolved in 1000 ml. ofethanol. 40 g. of 2,4-bis-dimethyla mino-6-chloro-1,3,

12 5-triazine, produced by reacting cyanuric chloride withdimethylamine, are then added to the solution and the whole is boiledwhile stirring. As soon as the reaction mixture has a neutral reaction,26 g. of concentrated sodium hydroxide solution are slowly addeddropwise.

The mixture is then further boiled until it again has a neutralreaction. The sodium chloride which has precipitated is filtered offfrom the hot solution. On cooling, the end product of the above formulacrystallises from the filtrate. It melts at 156 and gives good fastnessto industrial fumes.

If in the above example, instead of2,4-bis-dimethylamino-6-chlo1'o-1,3,5-triazine, equimolar amounts of2,4- bis-benzylamino-G-chlorotriazine or2,4-bis-cyclohexylamino-6-chlorotriazine are used then products areobtained which give similar fastness to industrial fumes.

6.9 g. of sodium are dissolved in 350 ml. of ethanol. 46 g. of the aminodichlorotriazine obtained according to Example 35 are then added and themixture is refluxed for 4 hours. During this time, a precipitate ofsodium chloride forms. The mixture is filtered and the filtrate cooledwhereupon the end product of the above formula crystallises out. It isfiltered off under suction and dried in vacuo at 70. The end productgives cellulose acetate dyeings good resistance to gas fading.

Example 40 CHrC z N N NC 0-SC2H5 OHPCI'IZ N l SC2H5 6.9 g. of sodium aredissolved in 250 m1. of propanol and the solution of 20 g. of ethylmercaptan in 200 ml. of propanol is added. 46 g. of the aminodichlorotriazine obtained according to Example 35 are then added to themixture and the whole is boiled for 4 hours. Sodium chlorideprecipitates which is filtered off. On cooling the filtrate the endproduct of the above formula crystallises out. It is filtered off undersuction, washed with a little ethanol and dried in vacuo at 70.

It makes cellulose acetate and cellulose ether dyeings resistant to gasfading.

Example 41 OHz-CHz 33 g. of 2-methyl-4,6-dichloro-1,3,5-triazine(produced according to US. Patent 1,911,689) are dissolved in 200 ml. ofbenzene. The solution of 64 g. of N-phenylpiperazine in 50 ml. ofbenzene is added dropwise to this solution at room temperature whilestirring. A slightly exothermic reaction takes place immediately and aprecipitate is formed. The reaction temperature is kept to 20 by coolingwith ice water. On completion of the dropwise addition, the mixture isheated to 30 within half an hour and it is then filtered. The filtrateis evaporated to dryness and the residue is recrystallised fromcyclohexane. In this way the end product of the above formula isobtained, M.P. 136. It gives cellulose acetate dyeings good resistanceto gas fading.

If instead of the 64 g. of N-phenyl piper-azine, equimolar amounts ofone of the compounds mentioned in Example 29 under (a) to (h) or inExample 35 under (a) to (d) are used'and otherwise the procedure givenin this example is followed, then end products which also give goodfastness to gas fading are obtained.

Compounds which also give good fastness to gas fading are obtained if,in the present example, instead of the 33 g. of2-methyl-4,6-dichloro-1,3,S-triazine, equimolar amounts of one of thefollowing compounds are used and otherwise the procedure given in theexample is followed.

(a) 2-ethyl-4,6-di=chloro-1,3,5-triazine,

(b) 2-cyclohexy1-4,6-dichloro-1,3,5-triazine,

(c) 2-benZyl-4,6-dichloro-1,3,5-triazine,

(d) 2-phenyl-4,6-dichloro-1,3,5-triazine,

(e) 2-methyl-4,6dibromo-1,3,5-triazine,

(f) 2- ,B-methoxy-ethyl -4,6-dichloro- 1,3,5 -triazine.

Example 42 3.4 g. of sodium are dissolved in 250 ml. of propanol, thesolution of g. of ethyl mercaptan in 100 ml. of propanol is added and 44g. of the diamino chlorotriazine obtained according to Example 36 areadded. The whole is then refluxed until the reaction mixture no longerhas a mimosa alkaline reaction. Precipitated sodium chloride is thenfiltered off. The end product of-the above formula crystallises out ofthe filtrate. The crystals are filtered off under suction and dried invacuo at 70. The substance melts at 158.

It gives cellulose ether dyeings good fastness to gas fading.

OHr-C H2 I NH:

5.9 g. of acetamide are dissolved in 100 ml. of abs. toluene. Thissolution is added dropwise, while stirring, to the suspension of 2.3 g.of pulverised sodium in 100 ml. of abs. toluene, the addition being madeat room temperature. The whole is stirred until all the sodium hasdisappeared. This suspension is then added dropwise at room temperatureto the solution of 29 g. of2-phenylpiperazinyl-4-amino-6-chloro-1,3,5-triazine in 150 ml. of abs.toluene. To complete the reaction, the mixture is finally heated to5060. The sodium chloride formed is then filtered off. The filtrate isevaporated to dryness in vacuo whereupon2-[(4'-phenyl-piperazinyl-(1'))]-4- amino-G-acetamido-1,3,5-triazine ofthe above formula is obtained.

If in the above example, equimolar amounts of benzoic acid amide areused instead of acetamide, the corresponding benz-oylamido triazinederivatives are obtained.

Example 44 Cellulose diacetate fabric is pre-treated for 30 minutes at40 with an aqueous/ethanolic dispersion which contains 0.7% (calculatedon the weight of the fabric) of the compound according to Example 25 and1% of the condensation product of cetyl alcohol and 20 mol ofethyleneoxide. An aqueous dispersion of 0.1% of the dyestuff C.I.Disperse Blue 3 (61505), 0.05% of the dyestufi C.I. Disperse Red 31(11250) and 0.125% of the dyestuff3-(4'-acylaminobenzene)-azo-4-hydroxy-1 methylbenzene is added to thisapplication bath.

The treatment bath is then heated from 40 to Within 30 minutes and keptfor another 45 minutes at this temperature. The sample is then rinsedand dried.

As a comparison, another sample of the same cellulose acetate fabric isdyed with the same dyestuffs in the same way as described above butWithout the auxiliary according to Example 25.

The dyed samples, together with a test fabric (gas fading control sampleNo. 1 of Test Fabrics Inc., 55, Vandam St., New York 13, NY.) are placedin a con tainer and exposed to the fumes of a gas flame at 4045 whileexcluding light (American Standard Method L14- 54, 1951) until the testfabric has changed from blue to red.

After exposure, the fabric treated with the compound according toExample 25 shows practically no change in shade Whereas the shade of thecomparative sample is very greatly changed. If in the above example thecompound of Example 34 is used, a similar good fastness of the dyeing isobtained.

Example 45 A solution of 15 g. of cellulose diacetate, 0.15 g. of thecompound according to Example 25, and 0.03 g. of 1-phenylamino-4-amino-anthraquinone in ml. of acetone is drawn into sheetsof about 0.2 mm. thickness.

As a comparison, corresponding sheets are produced without the compoundaccording to Example 25. Samples of these sheets together with anuntreated test fabric (gas fading control sample No. 1) are exposed tothe fumes of an open gas flame under the same conditions as given inExample 44.

After exposure, the sheet containing the compound according to Example25 shows no change in shade whereas the sample without this substancehas changed strongly from blue to pink.

Example 46 Yarn consisting of elastomeric polyurethane fiber (spandexfibers) commercially available under the trademark Lycra is impregnatedat 20 in a 1%-solution of the compound according to Example 22 inisopropanol. The yarn is squeezed out to 100% by weight and dried at50-60.

If this yarn is tested in the gas fading test according to the standardprocedure DIN 54,025 (testing with dilute nitrous fumes) it turnsconsiderably less yellow than un treated spandex yarn.

If in the above example the compound of Example 30 is used, a similargood fastness of the material is obtained.

n represents 1 or 2,

each of R R R R and R taken independently, is a number selected from thegroup consisting of hydrogen and lower alkyl,

each of R and R taken independently is a member selected from the groupconsisting of hydrogen, lower alkyl and pheny-l-lower alkyl,

each of the pairs R and R taken together and R and R taken togetherrepresents an a, 3-alkylene group of from 2 to 8 carbon atoms, and eachof the pairs R and R taken together and R and R taken togetherrepresents an a,6-n-butylene radical,

R represents a member selected from the group consisting of phenyl-loweralkyl, lower alkyl-phenyl-lower alkyl, halogeno-phenyl-lower alkyl,phenyl, halogeno- '15 phenyl, lower alkyl-phenyl, trifluor-omethylphenyl, phenoXy-phenyl, pheny-lthio-phenyl, naphthyl and cyclohexyl,each of X and X represents a member selected from the group consistingof chlorine, bromine, a radical R a radical -OR a radical SR and aradical wherein R is a member selected from the group consisting oflower alkyl, cyclohexyl, benzy-l, lower alkyl-benzyl, phenyl,lower-alkyl phenyl, lower alkoxy-lower-alkyl.

R is a member selected from the group consisting of hydrogen and loweralkyl, and

R is a member selected from the group consisting of hydrogen, loweralkyl and lower alkanoyl.

2. A compound of the formula 3. A compound of the formula CH3 CH3 4. Acompound of the formula 5. A compound of the formula CH3 CH3 6. Acompound of the formula Nit 8. A compound of the formula 9. A compoundof the formula CHq-OH; N

No references cited.

WALTER A. MODANCE, Primary Examiner.

J. M. FORD, Assistant Examiner.

1. A COMPOUND OF THE FORMULA